Stage 4 Harmonization á644ñ 1

Official August 1, 2019

Add the following:

▲
á644ñ CONDUCTIVITY OF SOLUTIONS
Portions of the chapter text that are national USP text and are not part of the harmonized text, are marked with symbols
(◆◆) to specify this fact.

INTRODUCTION

This chapter provides information on how to apply electrical conductivity measurements (hereafter referred to as
“conductivity”) of fluid solutions, including pure fluids. ◆This chapter does not replace the official Water Conductivity á645ñ
procedure, which is used to ensure the ionic purity of compendial waters such as Water for Injection, Purified Water, Pure
Steam condensate, and Sterile Water for Injection, among others.◆ This chapter is intended for ◆other◆ fluid applications
when conductivity is used to measure, monitor, or control chemical dispensing, chemical purity, ionic concentration, and
other applications where the ionic character of the fluid needs to be known or controlled.
Applications include, but are not limited to, solutions that may be used in clean-in-place, chromatography detection, ionic
solution preparations, endpoint detection, dosing, fermentation, and buffer production. In some cases, conductivity
measurements can be extended to pure organic fluids such as alcohols and glycols where a weak conductivity signal exists,
and the signal can be significantly increased if the organics become contaminated with water or salts. ◆ [NOTE—For
additional background information, see Theory and Practice of Electrical Conductivity Measurements of Solutions á1644ñ.] ◆
Conductivity is the measurement of the ability of a fluid to conduct electricity via its chemical ions. The ability of any ion
to electrically conduct is directly related to its ion mobility. Conductivity is directly proportional to the concentrations of ions
in the fluid, according to Equation 1:
all ions
� = 1000∑� ����

κ = conductivity (S/cm)
Ci = concentration of chemical ion i (mol/L)
λi = specific molar conductance of ion i (S · cm2/mol)

Although the SI unit S/m is the appropriate SI unit for conductivity, historically the unit S/cm has been selected by industry
as the accepted unit.
On the basis of Equation 1, conductivity is not ion selective because it responds to all ions. Furthermore, the specific molar
conductance of each ion is different. As a result, unless the percentage composition of ions of the solution is limited and
known, the precise concentrations of ionic species cannot be determined from conductivity measurements. However, for
examples such as a solution of a single salt or acid or base, such as a caustic solution used in cleaning, the precise
concentration can be directly determined. Despite the lack of ionic specificity, conductivity is a valuable laboratory and
process tool for measurement and control of total ionic content because it is proportional to the sum of the concentrations
of all ionic species (anions and cations) for diluted solutions as described in Equation 1. At higher concentrations, conductivity
measurements are not perfectly linear with concentration. Conductivity measurements cannot be applied to solids or gases,
but they can be applied to the condensate of gases.
Another variable that influences conductivity measurements is the fluid temperature. As the fluid temperature increases,
the ion conductance increases, making this physicochemical phenomenon the predominant reason for the temperature-
compensation requirement when testing conductive fluids.
The conductivity, κ, is proportional to the conductance, G (S), of a fluid between two electrodes (Equation 2):
�
�=�× � =�×�

κ = conductivity (S/cm)
G = conductance (S)
d = distance between the electrodes (cm)
A = area of the conducting electrodes (cm2)
K = cell constant (cm−1), which also equals the ratio of d/A

The resistivity p (Ω-cm) of the fluid is, by definition, the reciprocal of the conductivity (Equation 3):

ρ = 1/κ = 1 / (G x K) = R/K
ρ = resistivity (Ω-cm)
κ = conductivity (S/cm)
G = conductance (S)
K = cell constant (cm−1)
R = resistance (Ω), which is the reciprocal of the conductance, G

© 2018 The United States Pharmacopeial Convention All Rights Reserved.

2 á644ñ Stage 4 Harmonization
Official August 1, 2019

APPARATUS

An electrical conductivity measurement consists of the determination of resistance of the fluid between and around the
electrodes of the conductivity sensor. To achieve this measurement, the primary instrumentation is the resistance-measuring
circuit and the conductivity sensor, and they are usually connected by a cable when the sensor and the user interface are
separated.
The resistance measurement is made by applying an alternating current (AC, meaning the flow of electric charge
periodically reverses direction) voltage (or current) to the electrodes, measuring the current (or voltage), and calculating the
resistance according to Ohm’s law. The alternating source is used to prevent the polarization (collection of ions) at the
electrodes. Depending on the instrument, the measuring frequency of the measuring system adjusts automatically according
to the measuring conditions of the instrument, and there may be multiple resistance-measuring circuits embedded in the
measuring system. The resistance-measurement circuit may be embedded in the transmitter or in the sensor.
The conductivity sensor consists of at least two electrical conductors of a fixed size and geometry, separated by an
electrical insulator. The electrodes, insulator, and any other wetted materials should be constructed of materials that are
unreactive to fluids with which they may come into contact. Also, the sensor construction should withstand the
environmental conditions (process or ambient temperature, pressure, cleaning applications) that it would be subjected to.
Most conductivity sensors have temperature devices such as a platinum resistance temperature device (RTD) or negative
temperature coefficient (NTC) thermistor embedded inside the sensor, although external temperature measurement is
possible. The purpose of the temperature measurement is for temperature compensation of the conductivity measurement.

CELL CONSTANT DETERMINATION

The purpose of the sensor’s cell constant is to normalize the conductance (or resistance) measurement for the geometrical
construction of the two electrodes.
The cell constant is determined by immersing the conductivity sensor in a solution of known conductivity. Solutions of
known conductivity can be obtained by preparation of specific mixtures according to national authoritative sources or
procurement of commercially available certified and traceable standard solutions. These recipes or certified solutions can
range from 5 to 200,000 µS/cm, depending on the level of accuracy desired. Alternatively the cell constant is determined by
comparison to other reference conductivity measuring systems (also available as an accredited calibration service).
[NOTE—Conductivity measurements are not perfectly linear with concentration.]
The measured cell constant of the conductivity sensor must be within 5% of the nominal value indicated by the sensor
certificate, unless otherwise prescribed.
Modern conductivity sensors normally do not change their cell constant over their lifetime. If a change of the cell constant
is detected during calibration, a cleaning of the sensor is appropriate according to the manufacturer’s recommendations.
Following that, the calibration procedure should be repeated. Sometimes “memory effects” appear, particularly when
changing from high to low concentrations if the sensor is not well flushed.

CALIBRATION OF TEMPERATURE

In addition to verifying the sensor’s cell constant, the embedded temperature device (or external temperature device)
should be appropriately calibrated for the application to apply the temperature compensation algorithm accurately. The
temperature accuracy that is required depends on the criticality of the temperature to the application. An accuracy of ±1°
typically suffices.

CALIBRATION OF MEASUREMENT ELECTRONICS

The measurement circuit of the system is fundamentally an AC resistance measuring device. Appropriate verification
and/or calibration of the measuring circuit is required for measurement systems with signal transfer via analog cable. This is
accomplished by disconnecting the measuring circuit from the sensor’s electrodes, attaching traceable resistors of known
value with the cable of the measurement system to the measuring circuit, and verifying that the measured resistance agrees
with the resistor value to an acceptable level. A typical acceptance criterion for the resistance accuracy is <2% of the reading
at resistances >100 Ω, and increasing to 5% at lower resistances. However, the application criticality should ultimately
determine the desired accuracy.
For conductivity systems that cannot have the resistance-measuring circuit disconnected from the electrodes (e.g.,
measurement circuit and electrodes in one mutual housing), it may be difficult to directly adjust or verify the circuit
accuracy, depending on the sensor design. An alternative method of verifying the measurement system integrity is a system
calibration according to the procedures for the cell constant determination for each measuring circuit that is intended to be
used.
If verification/calibration of the sensor’s cell constant, temperature device, and measuring circuit are done at the same
service interval, the measuring circuit should be verified first, the temperature device next, and the cell constant last. Because
all of these parameters are typically very stable due to modern electronics and stable sensor construction, frequent
calibration (such as daily) is not usually required. Comparison to qualified reference systems is also a proper means of
calibration. Calibration is performed at appropriate intervals as defined in the quality management system.

© 2018 The United States Pharmacopeial Convention All Rights Reserved.

Stage 4 Harmonization á644ñ 3
Official August 1, 2019

TEMPERATURE COMPENSATION

Because the conductivity of a fluid is temperature dependent, temperature compensation of the conductivity
measurement is necessary unless otherwise prescribed (e.g., purified water, water for injection). An appropriate temperature
compensation algorithm will ensure that changes in the conductivity measurement can be ascribed to concentration
changes and not temperature changes. Conductivity measurements are normally referenced to 25°. A common form of
linear temperature compensation uses Equation 4:
��
�25 = 1 + � � − 25

κ25 = conductivity compensated to 25°

κT = conductivity at T
α = temperature coefficient of the conductivity
T = measured temperature

A temperature coefficient of 2.1% per 1° is commonly used for many salt solutions. Most salt-based solutions have linear
compensation factors ranging from 1.9% to 2.2% per 1°. Depending on the fluid samples, other forms of temperature
compensation may be appropriate. Non-linear temperature compensation data for a variety of solutions is widely available
(e.g., as described in ISO 7888 Water quality—Determination of electrical conductivity). In cases of very low conductivity (<10
µS/cm), such as purified pharmaceutical waters, two compensations need to be made. One is for the intrinsic conductivity of
water, and the other is for the other ionic species in water. These compensations are normally combined and embedded in
the microprocessor-controlled conductivity measurement systems. This is not supplied in all conductivity measurement
technologies.

CONDUCTIVITY MEASUREMENT OF FLUIDS

For off-line batch measurements, rinse the cleaned sensor with the fluid to be measured. Then immerse the sensor in the
fluid to be measured, and record the temperature and the temperature-compensated conductivity as required. Be sure that
the position of the sensor in the container does not affect the conductivity measurement, because the container walls can
affect the measurement for some electrode designs.
For continuous on-line or at-line measurements, install the cleaned sensor into the pipe, tank, or other containment vessel,
and flush, if necessary. Make sure proper installation procedures are applied to prevent bubbles or particles from collecting
between the electrodes. Be sure that the position of the sensor in the pipe or tank does not affect the conductivity
measurement, because the nearby surfaces can affect the measurement for some electrode designs.
Record the temperature and the temperature-compensated conductivity as required.
For all batch or continuous measurements, ensure that the wetted components of the sensor are compatible with the fluid
and the temperature to be measured.▲ USP 1-Aug-2019

© 2018 The United States Pharmacopeial Convention All Rights Reserved.